CN102250030B - Method for preparing 4-amino-6-methyl-1,2,4triazine-3-ketone - Google Patents
Method for preparing 4-amino-6-methyl-1,2,4triazine-3-ketone Download PDFInfo
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- CN102250030B CN102250030B CN 201010175508 CN201010175508A CN102250030B CN 102250030 B CN102250030 B CN 102250030B CN 201010175508 CN201010175508 CN 201010175508 CN 201010175508 A CN201010175508 A CN 201010175508A CN 102250030 B CN102250030 B CN 102250030B
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- triazines
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- methyl isophthalic
- isophthalic acid
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Abstract
The invention discloses a method for preparing 4-amino-6-methyl-1,2,4triazine-3-ketone hydrochloride by taking a hydrogen chloride methanol solution to replace a hydrogen chloride aqueous solution or a hydrogen chloride gas utilized by the prior art. According to the method provided by the invention, a series of problems of potential safety hazards and the like which are caused by directly utilizing the hydrogen chloride gas are avoided, and the environmental pollution caused by the industrial waste gas is reduced. The method disclosed by the invention has the advantages of low consumption of the hydrogen chloride, simplicity for operation and environment friendliness. The used raw materials are cheap and easy to obtain so that the method is an ideal industrial preparation method.
Description
Technical field
The invention belongs to the organic synthesis field, disclose a kind of novel method for preparing agricultural insecticide pymetrozine (Pymetrozine) intermediate, be specifically related to a kind of 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-ketone preparation method.
Technical background
Pymetrozine (Pymetrozine) is the non-lethal sterilant of a kind of new type heterocycle class, has the selectivity of mode of action uniqueness, height, without cross resistance, the characteristics such as environmentally safe, nuisanceless.At present, all use intermediate 4-amino-6-methyl isophthalic acid in the main synthetic method of preparation pymetrozine, 2,4 triazines-3-ketone, the synthetic of it is one of synthetic gordian technique of sterilant pymetrozine.4-amino-6-methyl isophthalic acid, the structural formula of 2,4 triazines-3-ketone is:
Patent US5648487, US5384403, US5324842, CA2029838, chemistry circular .2006,69 (9), 674 and fine-chemical intermediate .2001,31 (3), 18 bibliographical informations such as grade 4-amino-6-methyl isophthalic acid, the synthetic method of 2,4 triazines-3-ketone mainly contains following two kinds:
Method one: 4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, 2,4 triazines-3-ketone and concentrated hydrochloric acid reaction generate 4-amino-6-methyl isophthalic acid, and 2,4 triazines-3-keto hydrochloride are again through the product that neutralizes to get.The method yield is lower, and yield is the highest is no more than 92% for report among the patent US5648487.
Method two: to 4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, pass into hydrogen chloride gas in 2,4 triazines-3-ketone solution and prepare 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-keto hydrochloride obtain 4-amino-6-methyl isophthalic acid through neutralization again, 2,4 triazines-3-ketone.The method yield is higher, and US5384403 report yield can reach 99.2%, is the synthetic method of at present industrial main employing.It is that the hydrogenchloride consumption is larger that there is a larger drawback in the method.For example among the patent US538440,4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, the reinforced molecule number proportioning of 2,4 triazines-3-ketone and hydrogenchloride is 1: 1.5.Among the patent US5648487, reinforced molecular ratio is 1: 2.In addition, also there is following problem in the actual production:
1, commercial hydrogenchloride is the liquefied gas (50 normal atmosphere) that is stored in gas cylinder, and expensive, transportation, storage and operational safety hidden danger are larger; If adopt the on-the-spot hydrogenchloride that occurs such as concentrated hydrochloric acid or phosphorus trichloride, then waste gas spent acid quantity discharged is large.
When 2, passing into hydrogen chloride gas, if pressure surge easily produces the suck-back phenomenon, be not easy to operation.
Summary of the invention
The present invention seeks to for prior art at synthetic 4-amino-6-methyl isophthalic acid, 2, the problem such as the hydrogenchloride consumption that exists during 4 triazines-3-ketone is large, potential safety hazard is more, waste gas and waste liquid is large, provide that a kind of technique is simple, hydrogenchloride consumes low, stable reaction, product content and yield higher 4-amino-6-methyl isophthalic acid all, the new synthetic process of 2,4 triazines-3-ketone.
Contriver's develop goes out a kind of new preparation method: prepare 4-amino-6-methyl isophthalic acid with the alternative hydrochloride aqueous solution used in the prior art of hydrogen chloride methanol solution or hydrogen chloride gas, 2, the method of 4 triazines-3-keto hydrochloride, overcome the above-mentioned drawback that exists in the prior art, thereby realized purpose of the present invention.
Technical scheme of the present invention is as follows:
A kind of 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-ketone preparation method comprise: 1) .4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, 2,4 triazines-3-ketone and hcl reaction prepare 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-keto hydrochloride; 2). add in the alkali and 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-keto hydrochloride, preparation 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-ketone; Wherein the 1st) used hydrogenchloride adds with the form of hydrogen chloride methanol solution in the step reaction.
Preparation 4-amino-6-methyl isophthalic acid, the suitable reaction condition of 2,4 triazines-3-keto hydrochloride is: temperature of reaction 15-60 ℃, in 0.5～12 hour reaction times, the add-on of hydrogenchloride is 1.05-1.3 times of theoretical amount.
Preferred reaction conditions is: 20～50 ℃ of temperature of reaction, reaction times 1.5-6 hour, the add-on of hydrogenchloride was 1.1-1.25 times of theoretical amount.
The hydrogen chloride methanol solution that reacts used can be buied easily, and its concentration can guarantee to obtain satisfied reaction effect between 15%～35% (mass percent).
Prepare above-mentioned 4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, the used quantity of methyl alcohol of the methanol solution of 2,4 triazines-3-ketone should make raw material dissolve well, be beneficial to the reaction carry out smoothly.Require suitably to increase and decrease methanol usage according to concrete technology, this is those skilled in the art's common practise.
In and 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-keto hydrochloride, preparation 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-ketone is popular response as well known to those skilled in the art.
Adopt method of the present invention, 4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, 2,4 triazines-3-ketone transformation efficiency is greater than 99.8%, and yield is more than 99.3%.
The present invention synthesizes 4-amino-6-methyl isophthalic acid, and the series of problems such as potential safety hazard that brought when having avoided direct use hydrogen chloride gas in 2,4 triazines-3-ketone process reduce industrial gaseous waste to the pollution of environment.Hydrogenchloride raw material consumption is low, and technological operation is easy, and raw material is cheap and easy to get.Adopt this technique to obtain the 4-amino that content is 13-16% (mass percent)-6-methyl isophthalic acid, 2,4 triazines-3-ketone need not to purify or carry out other processing, can directly react with the 3-pyridylaldehyde to prepare the agricultural insecticide pymetrozine.Therefore, the invention provides a kind of desirable, environmental protection, be suitable for industrialized preparation method.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited to this.4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid wherein, the synthetic method of 2,4 triazines-3-ketone is circulated a notice of .2006 according to chemistry, the method preparation that provides in 69 (9), 674.
Embodiment 1:
In 1000 milliliters of reaction flasks, add 170 gram (1 mole) 4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acids, 2,4 triazines-3-ketone, 430 gram methyl alcohol, stirring and dissolving.At 35 ℃ of lower 30% hydrogen chloride methanol solution, 152 grams (1.25 moles) that drip, time for adding is 2 hours.Dropwise and continue insulation 0.5 hour, sampling analysis feed stock conversion 99.9%.Obtain 4-amino-6-methyl isophthalic acid, the methyl alcohol suspension liquid of 2,4 triazines-3-keto hydrochloride.
Above-mentioned material is transferred to neutrality with 50% aqueous sodium hydroxide solution, obtain feed liquid 845 grams.Analytical results: 4-amino-6-methyl isophthalic acid in the solution, 2,4 triazines-3-ketone content 15.1%, yield 99.8% (with 4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, 2,4 triazines-3-ketone meter).
Embodiment 2:
The hydrogen chloride methanol solution consumption changes 140 moles (1.15 moles) into, and soaking time is 5 hours, and other conditions and operation are with embodiment 1.Obtain feed liquid 826 grams, content 15.4%, yield 99.3% (with 4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, 2,4 triazines-3-ketone meter).
Embodiment 3:
Hydrogen chloride methanol solution content 25%, add-on 182.5 grams (1.25 moles), 20 ℃ of temperature of reaction, other conditions and operation are with embodiment 1.Get feed liquid 875 grams, content 14.5%, yield 99.2% (with 4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, 2,4 triazines-3-ketone meter).
Embodiment 4:
Hydrogen chloride methanol solution concentration 35%, add-on 115 grams (1.1 moles), 50 ℃ of temperature of reaction, other conditions and operation are with embodiment 1.Get feed liquid 796 grams, content 16%, yield 99.5% (with 4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, 2,4 triazines-3-ketone meter).
Claims (2)
1. 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-ketone preparation method comprise: 1) .4-acetylaminohydroxyphenylarsonic acid 6-methyl isophthalic acid, 2,4 triazines-3-ketone and hcl reaction prepare 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-keto hydrochloride;
2). add in the alkali and 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-keto hydrochloride, preparation 4-amino-6-methyl isophthalic acid, 2,4 triazines-3-ketone; It is characterized in that: described hydrogenchloride is the form adding with hydrogen chloride methanol solution, and its concentration is 15%～35% mass percent; Preparation 4-amino-6-methyl isophthalic acid, temperature of reaction 15-60 ℃ of 2,4 triazines-3-keto hydrochloride, 0.5～12 hour reaction times, the add-on of hydrogenchloride be theoretical amount 1.05-1.3 doubly.
2. according to preparation method claimed in claim 1, it is characterized in that: 20～50 ℃ of temperature of reaction, reaction times 1.5-6 hour, the add-on of hydrogenchloride was 1.1-1.25 times of theoretical amount.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010175508 CN102250030B (en) | 2010-05-17 | 2010-05-17 | Method for preparing 4-amino-6-methyl-1,2,4triazine-3-ketone |
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| CN 201010175508 CN102250030B (en) | 2010-05-17 | 2010-05-17 | Method for preparing 4-amino-6-methyl-1,2,4triazine-3-ketone |
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| CN102250030B true CN102250030B (en) | 2013-01-30 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5324842A (en) * | 1989-11-15 | 1994-06-28 | Ciba-Geigy Corporation | Process for the preparation of aminotriazine derivatives |
| CN1124736A (en) * | 1993-03-02 | 1996-06-19 | 希巴-盖吉股份公司 | Process for the preparation of 6-alkyl-4-(pyridin-3-yl-methyleneamino)-4,5-dihydro-1,2,4-triazin-3(2H)-one |
| CN1275570A (en) * | 1993-03-31 | 2000-12-06 | 诺瓦提斯公司 | Process for preparation of amino-triazine |
-
2010
- 2010-05-17 CN CN 201010175508 patent/CN102250030B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5324842A (en) * | 1989-11-15 | 1994-06-28 | Ciba-Geigy Corporation | Process for the preparation of aminotriazine derivatives |
| CN1124736A (en) * | 1993-03-02 | 1996-06-19 | 希巴-盖吉股份公司 | Process for the preparation of 6-alkyl-4-(pyridin-3-yl-methyleneamino)-4,5-dihydro-1,2,4-triazin-3(2H)-one |
| CN1275570A (en) * | 1993-03-31 | 2000-12-06 | 诺瓦提斯公司 | Process for preparation of amino-triazine |
Non-Patent Citations (2)
| Title |
|---|
| 王胜得等.高效杀虫剂吡蚜酮的合成研究及应用.《农药研究与应用》.2007,第11卷(第6期),第23-24页. |
| 高效杀虫剂吡蚜酮的合成研究及应用;王胜得等;《农药研究与应用》;20071231;第11卷(第6期);第23-24页 * |
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